CN110518214B - Nitrogen-hydrogen in-situ double-doped soft carbon/sodium vanadium phosphate composite material and preparation method and application thereof - Google Patents

Nitrogen-hydrogen in-situ double-doped soft carbon/sodium vanadium phosphate composite material and preparation method and application thereof Download PDF

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CN110518214B
CN110518214B CN201910823266.9A CN201910823266A CN110518214B CN 110518214 B CN110518214 B CN 110518214B CN 201910823266 A CN201910823266 A CN 201910823266A CN 110518214 B CN110518214 B CN 110518214B
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hydrogen
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vanadium phosphate
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何文
张合钰
张旭东
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Jiangsu Fuai Technology Development Co.,Ltd.
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Qilu University of Technology
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Abstract

The invention provides a nitrogen-hydrogen in-situ double-doped soft carbon/sodium vanadium phosphate composite material and a preparation method and application thereof. The invention uses bean or nut plant protein source to prepare slurry, then heats the slurry, adds sodium source, vanadium source and phosphorus source to react, then adjusts pH; finally, the nitrogen-hydrogen in-situ double-doped soft carbon/sodium vanadium phosphate composite material is prepared by hydrothermal reaction and calcination in inert atmosphere. Beans or nuts are used as a carbon source, a nitrogen and hydrogen source, an adsorbent, a complexing agent, a coagulant and a reaction carrier, and the mesoporous material compounded by nitrogen-hydrogen in-situ double-doped framework soft carbon and sodium vanadium phosphate with good electrochemical performance is prepared by mainly utilizing the composition, structure and performance characteristics of protein (amino acid) through adsorption, complexation and condensation of inorganic ions and ion groups, and through cracking reduction and N, H in-situ doping reaction. The carbon source used by the method has low cost, no toxicity and no pollution, and the synthesized composite material has excellent electrochemical properties such as specific capacity, rate capability, cycle performance and the like.

Description

Nitrogen-hydrogen in-situ double-doped soft carbon/sodium vanadium phosphate composite material and preparation method and application thereof
Technical Field
The invention relates to a nitrogen-hydrogen in-situ double-doped soft carbon/sodium vanadium phosphate composite material as well as a preparation method and application thereof, belonging to the technical field of positive electrode materials of sodium-ion batteries.
Background
Sodium ion batteries have attracted attention because of low sodium cost and abundant sources. Among the positive electrode materials of sodium ion batteries, sodium vanadium phosphate is considered to be one of the most potential positive electrode materials due to the advantages of low cost, open 3D framework NASICON structure and larger gap channels, and the like, and the sodium vanadium phosphate can accelerate the migration speed of sodium ions. However, the development and application of sodium vanadium phosphate are limited due to poor conductivity and electrochemical performance. Carbon doping of sodium vanadium phosphate has been proven to be an effective method for improving its conductivity and electrochemical properties, and at present, a carbon coating method is mostly adopted, for example, chinese patent document CN105336924A discloses a method for preparing a carbon-coated sodium vanadium phosphate positive electrode material, which uses glucose as a reducing agent and a carbon source, water as a dispersing agent, and NH as a dispersing agent4VO3、NaH2PO4·2H2Ball milling O and glucose in water, passing throughSpray drying and calcining to obtain the carbon-coated granular vanadium sodium phosphate cathode material, wherein the first charge-discharge specific capacity is up to 93.5mAh/g under the multiplying power of 1C, and the capacity retention rate is 97.7 percent after 1C circulation for 50 circles, so that the electrochemical performance is general, the preparation process is complex and the cost is high. Chinese patent document CN109768258A discloses an in-situ synthesis method of a sodium vanadium phosphate-carbon-graphene nano composite material and application thereof, wherein in the method, a suspension containing graphene is added during the synthesis of sodium vanadium phosphate, and the graphene-coated sodium vanadium phosphate/carbon composite material is synthesized through hydrothermal and calcination; when the material is used as a positive electrode material of a sodium-ion battery, the first discharge specific capacity is 98mAh/g at 1C, the electrochemical performance is general, the cost of the synthetic material is high due to the high price of graphene, and the problem of environmental pollution caused by the use of an organic solvent DMF exists.
Therefore, the search for a new technology of vanadium sodium phosphate/carbon composite materials with low cost, environmental protection and excellent performance is urgent and has important practical significance.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a nitrogen-hydrogen in-situ double-doped soft carbon/sodium vanadium phosphate composite material and a preparation method and application thereof. Beans or nuts are used as a carbon source, a nitrogen and hydrogen source, an adsorbent, a complexing agent, a coagulant and a reaction carrier, and the mesoporous material compounded by nitrogen-hydrogen in-situ double-doped framework soft carbon and sodium vanadium phosphate with good electrochemical performance is prepared by mainly utilizing the composition, structure and performance characteristics of protein (amino acid) through adsorption, complexation and condensation of inorganic ions and ion groups, and through cracking reduction and N, H in-situ doping reaction. The carbon source used by the method has low cost, no toxicity and no pollution, and the synthesized composite material has excellent electrochemical performance.
The invention is realized by the following technical scheme:
the composite material comprises a vanadium sodium phosphate phase and a nitrogen-hydrogen double-doped soft carbon skeleton compounded with the vanadium sodium phosphate, wherein the mass content of the vanadium sodium phosphate in the composite material is 80-90%, the mass content of carbon is 9-17%, the mass content of nitrogen is 0.5-2.5%, and the mass content of hydrogen is 0.3-1.6%; the composite material has a mesoporous structure, and the aperture of the composite material is 2-10 nm.
The invention also provides a preparation method of the nitrogen-hydrogen in-situ double-doped soft carbon/sodium vanadium phosphate composite material.
The preparation method of the nitrogen-hydrogen in-situ double-doped soft carbon/sodium vanadium phosphate composite material comprises the following steps:
(1) heating the plant protein source slurry at 80-100 ℃ for 0.2-1 h to obtain a solution A; the plant protein source is beans or nuts;
(2) adding a sodium source, a vanadium source and a phosphorus source into the solution A according to the molar ratio of Na to V to P of 3:2:3, mixing, stirring at 60-100 ℃ for 0.2-1 h for dissolving and reacting, and then adjusting the pH to 4-7 to obtain a mixture B;
(3) carrying out hydrothermal reaction on the mixture B at the temperature of 80-120 ℃ for 22-26 h to obtain a solidified body; drying and grinding the solidified body to obtain precursor powder;
(4) and heating the precursor powder to 300-450 ℃ at a heating rate of 4-7 ℃/min for heat treatment for 3-6 h in an inert atmosphere, heating to 700-900 ℃ at a heating rate of 2-5 ℃/min for heat treatment for 6-12 h, and cooling to obtain the nitrogen-hydrogen in-situ double-doped soft carbon/sodium vanadium phosphate composite material.
Preferably, in step (1), the vegetable protein source is soybean or black soybean.
Preferably, the preparation method of the plant protein source slurry in the step (1) comprises the following steps: firstly, beans or nuts are soaked in an ethanol water solution with the ethanol mass content of 10-20% for 4-8 hours, then the beans or nuts are ground into pulp by the ethanol water solution with the ethanol mass content of 10-20%, and the pulp is filtered by a sieve with 80-120 meshes to obtain the plant protein source pulp. Soaking beans or nuts in the ethanol water solution.
According to the invention, the concentration of the plant protein source slurry in the step (1) is preferably 0.05-0.12 g/ml; preferably, the concentration of the plant protein source slurry is 0.10 g/ml.
According to the invention, preferably, the sodium source in the step (2) is one of sodium dihydrogen phosphate or sodium carbonate; the vanadium source is one of ammonium metavanadate or vanadium pentoxide; the phosphorus source is one of ammonium dihydrogen phosphate or disodium hydrogen phosphate.
Preferably, in the mixture B in the step (2), the mass ratio of the plant protein source to the sodium vanadium phosphate is 0.1-1.6: 1; preferably, the mass ratio of the plant protein source to the sodium vanadium phosphate is 0.5-1.6: 1.
According to the invention, the dissolving and reaction temperature in the step (2) is preferably 80-100 ℃.
Preferably, according to the invention, acetic acid is used in step (2) to adjust the pH to 5.
According to the invention, the hydrothermal reaction temperature in the step (3) is preferably 100 ℃, and the hydrothermal reaction time is 24 h.
According to the invention, the drying temperature in the step (3) is preferably 60-100 ℃, and the drying time is preferably 3-8 h. Preferably, the drying temperature is 80 ℃ and the drying time is 6 h.
Preferably, according to the present invention, the grinding in step (3) is performed until the particle size of the precursor powder is 60-100 um.
Preferably, according to the present invention, the inert atmosphere in step (4) is nitrogen or argon.
Preferably, according to the invention, the heat treatment conditions in step (4) are: the temperature is raised to 350 ℃ at the heating rate of 5 ℃/min and is preserved for 4h, and then the temperature is raised to 800 ℃ at the heating rate of 3 ℃/min and is preserved for 8 h.
The invention also provides an application of the nitrogen-hydrogen in-situ double-doped soft carbon/sodium vanadium phosphate composite material.
The application of the nitrogen-hydrogen in-situ double-doped soft carbon/sodium vanadium phosphate composite material is used as a positive electrode material of a sodium ion battery; the specific application method is as follows:
(1) mixing the nitrogen-hydrogen in-situ double-doped soft carbon/sodium vanadium phosphate composite material with a binder and a conductive agent, fully grinding, adding an N-methyl pyrrolidone solvent, and stirring to obtain coating slurry;
(2) and (3) uniformly coating the coating slurry on an aluminum foil, drying to obtain a positive electrode plate, and using the electrode plate in a button type sodium ion battery.
According to the invention, the mass ratio of the nitrogen-hydrogen in-situ double-doped soft carbon/sodium vanadium phosphate composite material, the binder and the conductive agent in the step (1) is preferably 8:1: 1. The adhesive and the conductive agent can be conventional adhesives and conductive agents in the field. The addition amount of the N-methylpyrrolidone solvent is determined according to the prior art.
The technical principle of the invention is as follows: beans or nuts rich in protein (amino acid) are used as a carbon source, a nitrogen source, a hydrogen source, an adsorbent, a complexing agent, a coagulant and a reaction carrier, the C, N, H, O components of the protein (amino acid) and four-level amino acid double helix and folded super-large molecular long chain structure, and the adsorption, complexation, cohesiveness and other characteristics and characteristics of the protein (amino acid) are utilized, and the mesoporous material with the multilevel structure, the nitrogen-hydrogen double-doped three-dimensional network framework soft carbon and vanadium sodium phosphate composite is finally formed by adsorbing, complexing, assembling and coagulating inorganic ions and ionic groups, and under the auxiliary action of components such as fat, carbohydrate, cellulose, ethanol and the like, through hydrothermal solidification, pyrolysis reduction and N, H in-situ double-doping reaction. The nitrogen-hydrogen in-situ double-doped three-dimensional network framework soft carbon formed by the protein with the four-level amino acid double helix and the folded super-large molecular long chain structure can increase the electrochemical reaction defects and active sites of the electrode material, improve the conductivity of the electrode material, enhance the diffusion speed and sodium storage performance of sodium ions, have good compatibility with electrolyte and enable a charge-discharge potential platform to be stable; the composite framework structure can improve the strength and structural stability of the composite material, enhance the thermal stability and the charge-discharge impact resistance of the composite material and prevent the material from collapsing; the mesoporous structure is beneficial to ion transmission and electrolyte diffusion. The comprehensive factors can effectively improve the electrochemical performance of the electrode material.
The invention has the following beneficial effects:
the raw materials are cheap and easy to obtain, and the cost is low; toxic organic solvent is not used, and the method is green and environment-friendly.
Beans or nuts are used as a carbon source, and the nitrogen-hydrogen in-situ double-doped framework soft carbon and sodium vanadium phosphate composite mesoporous material is prepared by adsorption, complexation, flocculation, hydrothermal coagulation and cracking reduction reaction under specific conditions, wherein the mass content of the sodium vanadium phosphate is 80-90%, the mass content of carbon is 9-17%, the mass content of nitrogen is 0.5-2.5%, and the mass content of hydrogen is 0.3-1.6%; the mesoporous aperture is 2-10 nm. The nitrogen-hydrogen in-situ double-doped three-dimensional network framework soft carbon formed in the composite material increases the electrochemical reaction defects and active sites of the electrode material, improves the conductivity of the electrode material, enhances the diffusion speed and sodium storage performance of sodium ions, has good compatibility with electrolyte, and enables the finally obtained composite material to have a stable charge-discharge potential platform; and the composite framework structure can improve the strength and structural stability of the composite material, enhance the thermal stability and charge-discharge impact resistance of the composite material, prevent the material from collapsing, and ensure that the composite material has large charge-discharge capacity, high efficiency, good rate capability and good cycle performance. The mesoporous structure of the composite material is beneficial to ion transmission and electrolyte diffusion, and the electrochemical performance of the electrode material is further effectively improved.
The composite material is used as a positive electrode material of a sodium ion battery, and when the charging and discharging voltage is 2.0-4.3V, the first discharging specific capacity under 1C is 110 mAh/g; the first discharge specific capacity at 5C is 108 mAh/g; the first discharge specific capacity at 50 ℃ is 101mAh/g, the discharge specific capacity after 500 cycles at 50 ℃ is 94.2mAh/g, and the capacity retention rate is 93%; after 1000 cycles of circulation at 50 ℃, the specific discharge capacity is 88mAh/g, and the capacity retention rate is 87%; the data show that the composite material has excellent electrochemical properties such as specific capacity, rate capability, cycle performance and the like.
Drawings
FIG. 1 shows the N-H in-situ double-doped soft carbon/Na synthesized in example 1 of the present invention3V2(PO4)3XRD pattern of the composite; wherein the NVP/C curve refers to the nitrogen-hydrogen in-situ double-doped soft carbon/Na synthesized in example 13V2(PO4)3XRD curve and NVP curve of composite material are Na3V2(PO4)3XRD standard curve of (a).
FIG. 2 shows the N-H in-situ double-doped soft carbon/Na synthesized in example 1 of the present invention3V2(PO4)3Raman spectra of the composite material.
FIG. 3 shows an embodiment of the present invention1 synthesized nitrogen-hydrogen in-situ double-doped soft carbon/Na3V2(PO4)3Scanning electron micrographs of the composite.
FIG. 4 shows the N-H in-situ double-doped soft carbon/Na synthesized in example 1 of the present invention3V2(PO4)3Adsorption and pore size analysis of the composite.
FIG. 5 shows the N-H in-situ double-doped soft carbon/Na synthesized in example 1 of the present invention3V2(PO4)3Electrochemical cycling performance diagram of the composite material.
Detailed Description
The present invention will be further described with reference to the following detailed description of embodiments thereof, but not limited thereto, in conjunction with the accompanying drawings. The raw materials used in the examples are conventional raw materials and can be obtained commercially; the methods are prior art unless otherwise specified.
Example 1
A method for preparing a nitrogen-hydrogen in-situ double-doped soft carbon/sodium vanadium phosphate composite material comprises the following steps:
soaking 6g of soybeans in 40ml of 15% ethanol aqueous solution with mass concentration for 5h, grinding the soybeans into slurry by using 60m L15 wt% ethanol aqueous solution, sieving the slurry by using a 120-mesh sieve, heating the soybean milk at 100 ℃ for 0.5h to obtain solution A, adding 2.34g of ammonium metavanadate and 4.68g of sodium dihydrogen phosphate dihydrate into the solution A, stirring the solution A in a water bath at 80 ℃ for 0.5h to dissolve and react, then adjusting the pH value to 5 by using acetic acid to coagulate the system to obtain a mixture B of a condensate and liquid, putting the mixture B into a reaction kettle, carrying out hydrothermal heat preservation for 24h at 100 ℃, drying the obtained condensate at 80 ℃ for 6h, grinding the dried condensate solid to be less than 100um under nitrogen, carrying out heat preservation for 4h from room temperature to 350 ℃ according to 5 ℃/min, subsequently heating the condensate to 800 ℃ for 8h according to 3 ℃/min, and cooling to finally obtain the nitrogen-hydrogen in-situ double-doped framework soft carbon and sodium vanadium phosphate composite mesoporous material, namely NVC.
The XRD pattern of the composite material prepared in this example is shown in FIG. 1; the carbon content was 14.96 wt%, the nitrogen content was 1.35 wt%, and the hydrogen content was 0.95 wt% by test analysis.
The raman spectrum of the composite material prepared in this example is shown in figure 2,calculating the peak intensity ratio I of the material in the D band and the G band from the figure 2D/IGWhen the carbon content is 0.91 and less than 1, the carbon is soft carbon (soft carbon means amorphous carbon which can be graphitized at a high temperature of 2500 ℃ or higher).
The scanning electron microscope picture of the composite material prepared in this example is shown in fig. 3, and as can be seen from fig. 3, the structure of the composite material is a framework structure formed by compounding soft carbon and sodium vanadium phosphate.
The adsorption and pore size analysis chart of the composite material prepared in this example is shown in FIG. 3, and it can be seen from FIG. 3 that the pore size is 2-10 nm.
Electrochemical performance test
The composite material prepared in the embodiment is used as a positive electrode material of a sodium ion battery, and a positive electrode of the sodium ion battery is prepared by adopting a coating method. Weighing the prepared positive electrode material vanadium sodium phosphate composite material, acetylene black and polyvinylidene fluoride (PVDF) according to the mass ratio of 8:1:1, fully grinding and mixing the materials by using a mortar to obtain a mixture, adding an N-methyl pyrrolidone solvent into the mixture, and magnetically stirring the mixture for 12 hours to obtain mixture slurry; and coating the mixture slurry on an aluminum foil, drying at 60 ℃ for 6h, taking out, putting into a vacuum drying oven, vacuum-drying at 120 ℃ for 12h, naturally cooling, taking out the aluminum foil, and cutting into a wafer with the diameter of 1.5cm to obtain the positive electrode plate of the sodium-ion battery. Assembling the components in the glove box in the order of positive electrode shell, electrode plate, electrolyte, diaphragm, electrolyte, sodium sheet, gasket and negative electrode shell, and sealing the battery by using a sealing machine to obtain the CR2032 type button half-cell. The preparation method of the electrolyte comprises the following steps: sodium perchlorate is dissolved in a mixed solution with the volume EC: DEC: FEC of 1:1:0.05, and NaClO is added in the mixed solution4The concentration of the electrolyte is 1.0 mol/L, and a constant current charge and discharge test is carried out on the battery by a charge and discharge instrument, wherein the charge and discharge voltage is 2.0-4.3V.
When the charge-discharge voltage of the composite material prepared by the embodiment is 2.0-4.3V, the first discharge specific capacity under 1C is 110 mAh/g; the first discharge specific capacity under 5C is 108 mAh/g; the first discharge specific capacity under 50 ℃ is 101mAh/g, the discharge specific capacity after 500 cycles is 94.2mAh/g, and the capacity retention rate is 93%; after 1000 cycles at 50 ℃, the discharge specific capacity is 88mAh/g, and the capacity retention rate is 87%, which is shown in figure 4. The data show that the composite material prepared by the invention has excellent specific capacity, rate capability and cycling stability.
Example 2
A method for preparing a nitrogen-hydrogen in-situ double-doped soft carbon/sodium vanadium phosphate composite material comprises the following steps:
soaking 7g of soybeans in 50ml of 10% ethanol aqueous solution with the mass concentration for 4h, grinding the soybeans into slurry by using 60m L10 wt% ethanol aqueous solution, sieving the slurry by using a 80-mesh sieve, heating the soybean milk at 80 ℃ for 0.5h to obtain solution A, adding 2.34g of ammonium metavanadate and 4.68g of sodium dihydrogen phosphate dihydrate into the solution A, stirring the solution A in a water bath at 100 ℃ for 0.5h to dissolve and react, then adjusting the pH value to 6 by using acetic acid to coagulate the system to obtain a mixture B of a condensate and liquid, placing the mixture B into a reaction kettle, carrying out hydrothermal heat preservation for 22h at 120 ℃, drying the obtained condensate for 5h at 100 ℃, grinding the dried condensate solid to be less than 100um under nitrogen, carrying out heat preservation for 6h from room temperature to 300 ℃ according to 4 ℃/min, subsequently heating to 700 ℃ for 12h according to 2 ℃/min, and cooling to finally obtain the nitrogen-hydrogen in-situ double-doped framework soft carbon and sodium vanadium phosphate composite mesoporous material.
The electrochemical performance test is carried out according to the method of the embodiment 1, and the first discharge specific capacity of the cathode material at 1C is 96.5mAh/g, and the first discharge specific capacity at 50C is 65 mAh/g.
Example 3
A method for preparing a nitrogen-hydrogen in-situ double-doped soft carbon/sodium vanadium phosphate composite material comprises the following steps:
soaking 5g of black beans in 30ml of 20% ethanol aqueous solution by mass concentration for 8h, grinding the black beans into slurry by using 60m L20 wt% ethanol aqueous solution, sieving the slurry by using a 120-mesh sieve, heating the soybean milk at 100 ℃ for 0.5h to obtain solution A, adding 2.34g of ammonium metavanadate and 4.68g of sodium dihydrogen phosphate dihydrate into the solution A, stirring the solution A in a water bath at 100 ℃ for 0.5h to dissolve and react, then regulating the pH value to 4 by using acetic acid to coagulate the system to obtain a mixture B of a coagulum and liquid, putting the mixture B into a reaction kettle, carrying out hydrothermal heat preservation at 80 ℃ for 26h to obtain a coagulated body, drying the coagulated body at 60 ℃ for 8h, grinding the dried coagulated body to be less than 100um under nitrogen, carrying out heat preservation at 7 ℃/min from room temperature to 400 ℃ for 3h, then heating the mixture B at 5 ℃/min to 900 ℃ for 6h, and cooling to finally obtain the nitrogen-hydrogen in-situ double-doped framework soft carbon and sodium vanadium phosphate composite mesoporous material.
The electrochemical performance test is carried out according to the method of the embodiment 1, and the first discharge specific capacity of the cathode material at 1C is 99.5mAh/g, and the first discharge specific capacity at 50C is 75.7 mAh/g.
Comparative example 1
A preparation method of a carbon/sodium vanadium phosphate composite material comprises the following steps:
placing 2.34g ammonium metavanadate and 4.68g sodium dihydrogen phosphate dihydrate into a container containing 60ml distilled water, and stirring in water bath at 80 deg.C for 30min to obtain solution A; adding 3.96g of glucose into the solution A, and then stirring the solution A in a water bath at the temperature of 80 ℃ for 30min to obtain a mixed solution B; putting the mixed solution B into a reaction kettle, and carrying out hydrothermal heat preservation at 100 ℃ for 24 hours to obtain a precursor; drying the precursor at 80 ℃ for 2h, grinding the dried precursor into powder (the particle size is less than 100um), heating the powder to 350 ℃ from room temperature under nitrogen at the speed of 5 ℃/min, keeping the temperature for 4h, heating the powder to 800 ℃ at the speed of 3 ℃/min, keeping the temperature for 8h, and cooling the powder to obtain the carbon/sodium vanadium phosphate composite material.
The electrochemical performance test is carried out according to the method of the embodiment 1, and the first discharge specific capacity of the anode material 1C is 102 mAh/g; the first discharge specific capacity at 10C is 72.4mAh/g, and the discharge specific capacity after 100 cycles of circulation at 10C is only 42.7 mAh/g.
The comparative example selects glucose as the carbon source, the electrochemical performance of the comparative example is obviously inferior to that of the example 1, and particularly the high rate performance is poor, thereby illustrating the specificity and the superiority of the carbon source and the technical method thereof.
Comparative example 2
A preparation method of a carbon/sodium vanadium phosphate composite material comprises the following steps:
placing 2.34g ammonium metavanadate and 4.68g sodium dihydrogen phosphate dihydrate into a container containing 60ml distilled water, and stirring in water bath at 80 deg.C for 30min to obtain solution A; adding 2.280g of hemicellulose into the solution A, and then stirring in a water bath at 80 ℃ for 30min to obtain a mixed solution B; putting the mixed solution B into a reaction kettle, and carrying out hydrothermal heat preservation at 100 ℃ for 24 hours to obtain a precursor; drying the precursor at 80 ℃ for 2h, grinding the dried precursor into powder (the particle size is less than 100um), heating the powder to 350 ℃ from room temperature under nitrogen at the speed of 5 ℃/min, keeping the temperature for 4h, heating the powder to 800 ℃ at the speed of 3 ℃/min, keeping the temperature for 8h, and cooling the powder to obtain the carbon/sodium vanadium phosphate composite material.
The electrochemical performance test is carried out according to the method of the embodiment 1, and the first discharge specific capacity of the anode material at 1C is 86.6 mAh/g; the first discharge specific capacity at 10 ℃ is 57.2mAh/g, and the discharge specific capacity after 100 cycles of circulation at 10 ℃ is 44.9 mAh/g.
The comparative example selects hemicellulose as the carbon source, and the electrochemical performance of the carbon source is obviously inferior to that of the carbon source in the example 1, thereby illustrating the specificity and the superiority of the carbon source and the technical method thereof.
Comparative example 3
A preparation method of a carbon/sodium vanadium phosphate composite material comprises the following steps:
soaking 6g of soybeans in 40ml of water for 5 hours, grinding the soybeans into slurry by using 60m of L water, sieving the slurry with a 120-mesh sieve, heating the soybean milk at 100 ℃ for 0.5 hour to obtain a solution A, adding 2.34g of ammonium metavanadate and 4.68g of sodium dihydrogen phosphate dihydrate into the solution A, stirring the solution A in a water bath at 80 ℃ for 0.5 hour to dissolve the ammonium metavanadate and react, adjusting the pH value to 5 by using acetic acid to coagulate the system to obtain a mixture B of a coagulate and a liquid, putting the mixture B into a reaction kettle, carrying out hydrothermal heat preservation at 100 ℃ for 24 hours to obtain a coagulate, drying the coagulate at 80 ℃ for 6 hours, grinding the coagulate to be less than 100 microns, carrying out heat preservation at 5 ℃/min to 350 ℃ for 4 hours, heating at 3 ℃/min to 800 ℃ for 8 hours, and cooling to obtain the carbon/sodium vanadium phosphate composite.
The electrochemical performance test is carried out according to the method of the embodiment 1, the first discharge specific capacity of the cathode material at 50 ℃ is 58mAh/g, the discharge specific capacity after 100 cycles is 43.5mAh/g, and the capacity retention rate is 75%.
In the comparative example, water is selected to replace ethanol solution to soak and polish soybeans on the basis of example 1, the electrochemical performance of the soybean is obviously inferior to that of example 1, and the specificity and the superiority of the ethanol and the solution thereof are illustrated.
Comparative example 4
A preparation method of a carbon/sodium vanadium phosphate composite material comprises the following steps:
soaking 6g of soybeans in 40ml of 15% ethanol aqueous solution with the mass concentration for 5h, grinding the soybeans into slurry by using 60m L15 wt% ethanol aqueous solution, sieving the slurry by using a 120-mesh sieve, heating the soybean milk at 65 ℃ for 8min to obtain solution A, adding 2.34g of ammonium metavanadate and 4.68g of sodium dihydrogen phosphate dihydrate into the solution A, stirring the solution A in a water bath at 50 ℃ for 6min, adjusting the pH value to 3 by using acetic acid to obtain mixture B, putting the mixture B into a reaction kettle, carrying out hydrothermal heat preservation at 70 ℃ for 20h, taking out the mixture, drying the mixture at 80 ℃ for 6h, grinding the mixture to be less than 100um, carrying out heat preservation at 5 ℃/min from room temperature to 350 ℃ for 4h under nitrogen, heating at 3 ℃/min to 800 ℃ for 8h, and cooling to finally obtain the carbon/sodium vanadium phosphate composite material.
The electrochemical performance test is carried out according to the method of the embodiment 1, the first specific discharge capacity of the cathode material at 50 ℃ is 46.5mAh/g, the specific discharge capacity after 100 cycles is 31.2mAh/g, and the capacity retention rate is 67%.
This comparative example changes part of the preparation conditions on the basis of example 1, and its electrochemical performance is significantly inferior to that of example 1, thus illustrating the specificity and superiority of the preparation conditions of the present invention.

Claims (7)

1. A preparation method of a sodium ion battery anode material nitrogen-hydrogen in-situ double-doped soft carbon/sodium vanadium phosphate composite material is characterized in that the composite material comprises a sodium vanadium phosphate phase and a nitrogen-hydrogen double-doped soft carbon skeleton compounded with the sodium vanadium phosphate, wherein the mass content of the sodium vanadium phosphate in the composite material is 80-90%, the mass content of carbon is 9-17%, the mass content of nitrogen is 0.5-2.5%, and the mass content of hydrogen is 0.3-1.6%; the composite material has a mesoporous structure, and the aperture of the composite material is 2-10 nm;
the preparation method comprises the following steps:
(1) heating the plant protein source slurry at 80-100 ℃ for 0.2-1 h to obtain a solution A; the plant protein source is beans or nuts;
the preparation method of the plant protein source slurry comprises the following steps: firstly, beans or nuts are soaked in an ethanol water solution with the ethanol mass content of 10-20% for 4-8 hours, then the beans or nuts are ground into pulp by the ethanol water solution with the ethanol mass content of 10-20%, and the pulp is filtered by a sieve with 80-120 meshes to obtain plant protein source pulp;
(2) adding a sodium source, a vanadium source and a phosphorus source into the solution A according to the molar ratio of Na to V to P of 3:2:3, mixing, stirring at 60-100 ℃ for 0.2-1 h for dissolving and reacting, and then adjusting the pH to 4-7 to obtain a mixture B;
(3) carrying out hydrothermal reaction on the mixture B at the temperature of 80-120 ℃ for 22-26 h to obtain a solidified body; drying and grinding the solidified body to obtain precursor powder;
(4) and heating the precursor powder to 300-450 ℃ at a heating rate of 4-7 ℃/min for heat treatment for 3-6 h in an inert atmosphere, heating to 700-900 ℃ at a heating rate of 2-5 ℃/min for heat treatment for 6-12 h, and cooling to obtain the nitrogen-hydrogen in-situ double-doped soft carbon/sodium vanadium phosphate composite material.
2. The method for preparing the nitrogen-hydrogen in-situ double-doped soft carbon/sodium vanadium phosphate composite material of the positive electrode material of the sodium-ion battery as claimed in claim 1, wherein the plant protein source in the step (1) is soybean or black bean.
3. The preparation method of the sodium-ion battery positive electrode material nitrogen-hydrogen in-situ double-doped soft carbon/sodium vanadium phosphate composite material according to claim 1, wherein the concentration of the plant protein source slurry in the step (1) is 0.05-0.12 g/ml.
4. The preparation method of the sodium-ion battery cathode material nitrogen-hydrogen in-situ double-doped soft carbon/sodium vanadium phosphate composite material according to claim 1, wherein in the mixture B in the step (2), the mass ratio of the plant protein source to the sodium vanadium phosphate is 0.1-1.6: 1.
5. The method for preparing the nitrogen-hydrogen in-situ double-doped soft carbon/sodium vanadium phosphate composite material of the positive electrode material of the sodium-ion battery according to claim 1, wherein the step (2) comprises one or more of the following conditions:
a. the sodium source is one of sodium dihydrogen phosphate or sodium carbonate; the vanadium source is one of ammonium metavanadate or vanadium pentoxide; the phosphorus source is one of ammonium dihydrogen phosphate or disodium hydrogen phosphate;
b. the dissolving and reaction temperature is 80-100 ℃;
c. the pH was adjusted to 5 with acetic acid.
6. The method for preparing the nitrogen-hydrogen in-situ double-doped soft carbon/sodium vanadium phosphate composite material of the positive electrode material of the sodium-ion battery according to claim 1, wherein the step (3) comprises one or more of the following conditions:
a. the hydrothermal reaction temperature is 100 ℃, and the hydrothermal reaction time is 24 hours;
b. the drying temperature is 60-100 ℃, and the drying time is 3-8 h;
c. and grinding until the particle size of the precursor powder is 60-100 um.
7. The preparation method of the sodium-ion battery positive electrode material nitrogen-hydrogen in-situ double-doped soft carbon/sodium vanadium phosphate composite material according to claim 1, wherein the heat treatment conditions in the step (4) are as follows: the temperature is raised to 350 ℃ at the heating rate of 5 ℃/min and is preserved for 4h, and then the temperature is raised to 800 ℃ at the heating rate of 3 ℃/min and is preserved for 8 h.
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